This article describes for the first time the direct observation of the nucleation and growth process of closely packed silica nanowires via a vapor-liquid-solid (VLS) mechanism by using tin (Sn) as a catalyst. Initially, Sn particles formed alloy liquids, followed by the nucleation of short silica nanowires, and closely packed silica nanowires finally formed. Interestingly, our results indicated that Sn has different catalytic behavior for nanowire growth than commonly used metal catalysts such as Au and Fe. The structural features associated with different growth stages were monitored by SEM, TEM, EDX, and XPS analysis. A possible mechanism for the formation of closely packed silica nanowires is proposed.